WO2013014081A1 - Catalyst for the conversion of oxygenates to olefins and a process for preparing said catalyst - Google Patents

Catalyst for the conversion of oxygenates to olefins and a process for preparing said catalyst Download PDF

Info

Publication number
WO2013014081A1
WO2013014081A1 PCT/EP2012/064300 EP2012064300W WO2013014081A1 WO 2013014081 A1 WO2013014081 A1 WO 2013014081A1 EP 2012064300 W EP2012064300 W EP 2012064300W WO 2013014081 A1 WO2013014081 A1 WO 2013014081A1
Authority
WO
WIPO (PCT)
Prior art keywords
catalyst
suz
zeolite
conversion
oxygenates
Prior art date
Application number
PCT/EP2012/064300
Other languages
French (fr)
Inventor
Shewangizar TEKETEL
Stian SVELLE
Pablo Beato
Original Assignee
Haldor Topsøe A/S
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Haldor Topsøe A/S filed Critical Haldor Topsøe A/S
Priority to US14/234,370 priority Critical patent/US9616417B2/en
Priority to CN201280036323.5A priority patent/CN103842081B/en
Publication of WO2013014081A1 publication Critical patent/WO2013014081A1/en

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/06—Washing
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/20—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms
    • C07C1/22—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only oxygen atoms as heteroatoms by reduction
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/16—After treatment, characterised by the effect to be obtained to increase the Si/Al ratio; Dealumination
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/30—After treatment, characterised by the means used
    • B01J2229/36—Steaming
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/30—After treatment, characterised by the means used
    • B01J2229/37—Acid treatment
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
    • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • C07C2529/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65

Definitions

  • the present invention relates to a catalyst, which is suit ⁇ able for use in the process where oxygenates, i.e. chemical compounds containing oxygen as part of their structure (e.g. alcohols or ethers) are converted to olefins.
  • oxygenates i.e. chemical compounds containing oxygen as part of their structure (e.g. alcohols or ethers) are converted to olefins.
  • a meth- od for the formation of the catalyst is also provided.
  • the invention concerns a catalyst for the conversion of oxygenates to olefins, said catalyst being based on SUZ-4 zeolite.
  • the SUZ-4 zeolite is modified in a number of ways with the purpose to yield a catalyst with improved properties for the conversion of oxygenates to olefins .
  • the SUZ-4 zeolite has been given the three-letter IUPAC designation code SZR.
  • the 10-membered ring channels of the SUZ-4 zeolite are the main straight channels in the framework, and they are interconnected by zig-zag 8-ring channels.
  • the 10-ring straight channels of the SUZ-4 zeo- lite have dimensions of 4.6 x 5.2 A, i.e.
  • EP 0 706 984 Al discloses the catalytic use of SUZ-4 zeolite for the isomerisation of hydrocarbons, and in US 6,514,470 B2 (University of California) a large number of aluminium-silicate materials, including SUZ-4 ze ⁇ olite, are used as catalysts for lean burn exhaust abate ⁇ ment.
  • JP 2009-233620 A describes the use of SUZ-4 zeolite in an SCR catalyst with the objective to give the catalyst improved hydrothermal durability.
  • the invention concerns a catalyst for the conversion of oxygenates to olefins, said catalyst consisting essentially of a selected SUZ-4 zeolite.
  • the catalyst according to the invention is characterised in that the zeolite has a Si/Al ratio of at least 20, preferably between 20 and 500. The most preferred Si/Al ratio in the zeolite is between 20 and 100.
  • step (b) increasing the Si/Al ratio to 20 or above by con- tacting the product of step (a) with water vapour at elevated temperatures.
  • step (b) is preferably performed at a temperature of 400-700°C. Furthermore it is preferred to perform step (b) for 1-12 hours by feeding 1-20 g 3 ⁇ 40 per g of catalyst per hour.
  • the SUZ-4 catalyst resulting from step (b) of the process is preferably washed with an aqueous acid solution.
  • the catalyst according to the invention is used for the conversion of oxygenates to olefins.
  • the oxygenates to be converted to olefins are preferably selected from the group consisting of CI to C4 alcohols.
  • the most preferred oxygen- ate to be converted to an olefin is methanol.
  • Fig. 5 shows GC-MS chromatograms of SAPO-34, SUZ-4, and ZSM-5 catalysts tested under identical reaction conditions after 5 minutes on stream.
  • the SUZ-4 zeolite-based catalyst is synthesized in a manner known per se by preparing (i) a solution of Al-wire in aqueous MOH, where M is an alkali metal, (ii) a 25 wt% so ⁇ lution of tetraethylammonium hydroxide (TEAOH) and (iii) a 40 wt% solution of Ludox-AS 40, mixing the solutions (i)- (iii) at 60°C and crystallizing the resultant gel at 160°C with stirring, followed by (iv) ion-exchange to remove the M ions completely from the material and (v) calcination to obtain the zeolite in hydrogen form.
  • MOH tetraethylammonium hydroxide
  • this standard method gives a H-SUZ-4 catalyst with high density of acid sites, and it deactivates very rapidly during oxygenate (methanol) conversion to olefins.
  • oxygenate methanol
  • the drawback is the rapid deactiva- tion.
  • the Si/Al ratio is then adjusted to the desired value by changing the amount of Al-wire dissolved in the aqueous MOH solution (i) .
  • the Si/Al ratio can also be ad- justed to the desired value another way, i.e. by contacting the product with water vapour at elevated temperatures (so- called "steaming" .
  • the steaming is preferably performed for a period of 1-12 hours by feeding 1-20 g 3 ⁇ 40 per g of catalyst per hour at a temperature of 400-700°C. After the steaming the resulting SUZ-4 catalyst is washed with an aqueous acid solution.
  • the present invention is related to the use of the above- mentioned SUZ-4 zeolite material in the conversion of oxy- genates, especially methanol/dimethyl ether (DME) , to olefins.
  • SUZ-4 zeolite material in the conversion of oxy- genates, especially methanol/dimethyl ether (DME)
  • DME methanol/dimethyl ether
  • SZR topology consisting of a 3-dimensional channel system of straight 10-rings and zig-zag 8-rings, a surprisingly high selectivity (60-70%) to light olefins (ethylene and propylene) is observed.
  • a by-product approximately 10-20%) , olefins with a hydrocar ⁇ bon chain length in the gasoline range are obtained.
  • the selectivity to aromatic hydrocarbons is typically below 2%.
  • the calcined material as prepared was sub ⁇ jected to ion-exchange three times with an aqueous IN NH 4 NO 3 solution under reflux, washed with deionized wa ⁇ ter, dried at 120°C for 3 hours and then calcined at 550°C for 12 hours.
  • the synthesis conditions used are
  • H.S. means horizontal stirring
  • SUZ-4a means SUZ-4 + amorphous .
  • X-ray diffraction (XRD) data were analyzed using EVA 8.0, developed by SOCABIM. The diffraction pattern was compared with the data in the powder diffraction file (PDF) database compiled and revised by Joint Committee on Powder Diffraction Standards International Centre. Surface area
  • the BET surface area of the SUZ-4 catalysts was deter ⁇ mined by nitrogen adsorption at a temperature of 77 K using a BELSORP-mini II instrument. Prior to the measurement the catalyst was pretreated for 5 hours (out- gassing for 1 hour at 80°C and for 4 hours at 300°C) .
  • the calcined SUZ-4 catalysts were tested for the MTH reaction using a fixed bed reactor. 50 mg of catalysts and temperatures between 350 and 450 °C were used. The catalysts were pressed, gently crushed and sieved to a particle size of 0.25-0.42 mm. Before each test, the catalysts were calcined in situ at 550°C (see above) under a flow of oxygen for 1 hour. Helium was used as a carrier gas and methanol was fed using a bubble satura- tor placed in a water bath at 20°C. A methanol feed rate (expressed as WHSV, i.e. weight hourly space ve ⁇ locity, which is defined as the weight of feed flowing per unit weight of the catalyst per hour) of 2.05 gg _1 h _1 was used. The reaction products were analyzed by GC and GC-MS .
  • the GC analyses were performed using an on-line gas chromatograph (Agilent 6890 A with FID) using a Supelco SPB-5 capillary column (60m, 0.530 mm i.d., stationary phase thickness 3ym) . The temperature was programmed between 45 and 260°C with a heating rate of 25 °C min -1 (hold time 5 min at 45°C and 16 min at the final tem ⁇ perature) .
  • GC-MS analyses were performed using a HP 6890 gas chromatograph equipped with a GS-GASPRO column (60m, 0.32 mm) and a HP-5973 Mass Selective Detector. Each analysis took 40 minutes, and the temperature was programmed between 100 and 250 °C with a heating rate of 10°C min -1 (hold time 10 min at 100°C and 15 min at 250°C) . (c) Results
  • Fig. 3 displays (a) TEM overview micrograph, (b) Micrograph and diffraction image (insert) of random crystallite.
  • Fig. 5 displays GC-MS chromatograms of the methanol to hydrocarbon reaction over different zeolites, reaction carried out under identical conditions.

Abstract

A catalyst for the conversion of oxygenates, such as alcohols or ethers, to olefins consists essentially of a selected SUZ-4 zeolite that has a Si/A1 ratio of at least 20, preferably between 20 and 500, especially between 20 and 100. The basic SUZ-4 zeolite is prepared in a manner known per se, whereafter the Si/A1 ratio is increased to the desired value. The selected SUZ-4 zeolite catalyst of the invention has a longer life time and a better product selectivity than the conventional/standard SUZ-4 zeolite catalysts.

Description

Catalyst for the conversion of oxygenates to olefins and a process for preparing said catalyst
Technical Field
The present invention relates to a catalyst, which is suit¬ able for use in the process where oxygenates, i.e. chemical compounds containing oxygen as part of their structure (e.g. alcohols or ethers) are converted to olefins. A meth- od for the formation of the catalyst is also provided.
More specifically the invention concerns a catalyst for the conversion of oxygenates to olefins, said catalyst being based on SUZ-4 zeolite. The SUZ-4 zeolite is modified in a number of ways with the purpose to yield a catalyst with improved properties for the conversion of oxygenates to olefins .
Background to the Invention
SUZ-4 zeolite has been given the three-letter IUPAC designation code SZR. The framework of the SUZ-4 zeolite consists of 4-, 5-, 6-, 8- and 10-membered rings of 3- dimensional channel systems. It has an ortho-rhombic unit cell with dimensions of a = 18.8696, b = 14.4008 and c = 7.5140 A, respectively. The 10-membered ring channels of the SUZ-4 zeolite are the main straight channels in the framework, and they are interconnected by zig-zag 8-ring channels. The 10-ring straight channels of the SUZ-4 zeo- lite have dimensions of 4.6 x 5.2 A, i.e. notably smaller than the 10-ring channels found in the ZSM-5 zeolite (5.3 x 5.5 and 5.4 x 5.6 A) . Within the catalyst area, the SUZ-4 zeolite is known to be a selective and stable dehydration catalyst in the process for producing dimethyl ether from methanol (Jiang, S. et al., Chemistry Letters 33, no. 8, 1048 (2004)).
According to US 6,936,562 B2 (General Motors Corp.), certain metal-exchanged SUZ-4 zeolites have been prepared which have catalytic activity in the reduction of NOx in the exhaust gas from a hydrocarbon or alcohol fuelled en¬ gine .
Similar hydrothermally-stable catalysts based on substi¬ tuted SUZ-4 zeolites are described in the related US
6,645,448 B2 (General Motors Corp.), and in US 5,118,483 B2 (British Petroleum Co.) various crystalline forms of the SUZ-4 zeolite based on crystalline (metallo) silicates are described. It should be noted that - with reference to e.g. US 5,118,483 - the standard methods for forming SUZ-4 zeo- lites will usually provide thermochemically-preferred Si/Al stoichiometries , regardless of the molar ratios of the Si and Al components in the starting materials.
EP 0 706 984 Al (BP Chemicals Ltd.) discloses the catalytic use of SUZ-4 zeolite for the isomerisation of hydrocarbons, and in US 6,514,470 B2 (University of California) a large number of aluminium-silicate materials, including SUZ-4 ze¬ olite, are used as catalysts for lean burn exhaust abate¬ ment. JP 2009-233620 A (Tosoh Corp.) describes the use of SUZ-4 zeolite in an SCR catalyst with the objective to give the catalyst improved hydrothermal durability. Most recently, variants of the methanol to olefins (MTO) process have been disclosed in EP 1 963 241 A2 and in WO 2008/042616 A2 (both to UOP LLC) . One of the main challenges within the field of MTO cataly¬ sis is that the known catalysts have a very limited life span, requiring continuous regeneration at elevated temperature which eventually lead to irreversible damage to the catalyst. According to the inventors, this is also the case with the SUZ-4 zeolite-based catalysts, because the life span of the current SUZ-4 zeolite-based catalyst pre¬ pared using the standard methods in the MTO catalysis field does not exceed that of other catalysts such as silicoalu- minophosphate molecular sieves (e.g. SAPO-34). However, it has now surprisingly been found that the life span of the SUZ-4 zeolite-based catalyst for MTO use can be markedly improved by either modification of the zeolite acidity (i.e. by increasing the Si/Al ratio, partial ion-exchange of alkali counter-ions)
Summary of the Invention
The invention concerns a catalyst for the conversion of oxygenates to olefins, said catalyst consisting essentially of a selected SUZ-4 zeolite. The catalyst according to the invention is characterised in that the zeolite has a Si/Al ratio of at least 20, preferably between 20 and 500. The most preferred Si/Al ratio in the zeolite is between 20 and 100.
Furthermore, the invention concerns a process for the preparation of the catalyst, said method comprising the steps of: (a) providing a conventional/standard SUZ-4 zeolite having a Si/Al ratio of less than 20, and
(b) increasing the Si/Al ratio to 20 or above by con- tacting the product of step (a) with water vapour at elevated temperatures.
In the above process, step (b) is preferably performed at a temperature of 400-700°C. Furthermore it is preferred to perform step (b) for 1-12 hours by feeding 1-20 g ¾0 per g of catalyst per hour.
The SUZ-4 catalyst resulting from step (b) of the process is preferably washed with an aqueous acid solution.
The catalyst according to the invention is used for the conversion of oxygenates to olefins. The oxygenates to be converted to olefins are preferably selected from the group consisting of CI to C4 alcohols. The most preferred oxygen- ate to be converted to an olefin is methanol.
Brief Description of the Figures
Figure 1 shows the XRD diffraction profile of SUZ-4 having gel Si/Al = 8 and 13.
Figure 2 shows an SEM image of SUZ-4 having Si/Al = 8 in the synthesis gel. Figure 3 shows a TEM image of an SUZ-4 zeolite-based cata¬ lyst having Si/Al = 8 in the synthesis gel. Figure 4 shows the BET isotherm of SUZ-4 having gel Si/Al = 8 in the synthesis gel.
Fig. 5 shows GC-MS chromatograms of SAPO-34, SUZ-4, and ZSM-5 catalysts tested under identical reaction conditions after 5 minutes on stream. NB : CI is not included in the chromatogram. (400 °C and WHSV = 2.05 gg_1h_1)
Detailed description of the invention
According to the invention the selected SUZ-4 zeolite has a Si/Al ratio of at least 20, preferably between 20 and 500 as determined using SEM-EDX, ICP and ammonia TPD. A more preferred Si/Al ratio is between 20 and 100.
The SUZ-4 zeolite-based catalyst is synthesized in a manner known per se by preparing (i) a solution of Al-wire in aqueous MOH, where M is an alkali metal, (ii) a 25 wt% so¬ lution of tetraethylammonium hydroxide (TEAOH) and (iii) a 40 wt% solution of Ludox-AS 40, mixing the solutions (i)- (iii) at 60°C and crystallizing the resultant gel at 160°C with stirring, followed by (iv) ion-exchange to remove the M ions completely from the material and (v) calcination to obtain the zeolite in hydrogen form. According to the in- vention, this standard method gives a H-SUZ-4 catalyst with high density of acid sites, and it deactivates very rapidly during oxygenate (methanol) conversion to olefins. It should be noted that the conversion of methanol to olefins is novel in this work, the drawback is the rapid deactiva- tion. Thus, the Si/Al ratio is then adjusted to the desired value by changing the amount of Al-wire dissolved in the aqueous MOH solution (i) . The Si/Al ratio can also be ad- justed to the desired value another way, i.e. by contacting the product with water vapour at elevated temperatures (so- called "steaming") . The steaming is preferably performed for a period of 1-12 hours by feeding 1-20 g ¾0 per g of catalyst per hour at a temperature of 400-700°C. After the steaming the resulting SUZ-4 catalyst is washed with an aqueous acid solution.
While it is known from the above citations that SUZ-4 zeo- lites may be used as catalysts in various contexts, the specific use of SUZ-4 zeolite materials as catalysts in the conversion of oxygenates to olefins is novel. Thus, the present invention is related to the use of the above- mentioned SUZ-4 zeolite material in the conversion of oxy- genates, especially methanol/dimethyl ether (DME) , to olefins. Due to the unique topology (SZR topology), consisting of a 3-dimensional channel system of straight 10-rings and zig-zag 8-rings, a surprisingly high selectivity (60-70%) to light olefins (ethylene and propylene) is observed. As a by-product (approximately 10-20%) , olefins with a hydrocar¬ bon chain length in the gasoline range are obtained. The selectivity to aromatic hydrocarbons is typically below 2%.
As a consequence of the selectivities observed, the
catalyst has a high potential to be used cL S cL C3.talyst for the production of light olefins (ethylene and pro¬ pylene) with a gasoline fraction having a low content of aromatic compounds as a co-product. Methane, which is also regarded as co-product during olefin produc- tion, could be used as a source for the necessary ex¬ ternal thermal energy for the MTO process. The present invention will now be illustrated further in the following examples.
Example 1
(A) Synthesis of SUZ-4 zeolite using the standard method
An SUZ-4 zeolite was synthesized according to the procedure published by S. Jiang et al . , Chemistry Letters 33, no. 8, 1048 (2004) .
The following solutions were prepared:
(a) 0.4 g Al-wire dissolved in a KOH solution (3.3 g KOH in 50.6 g H20)
(b) 7.93 g TEAOH (25 wt%)
(c) 18.23 g LUDOX AS-40 (40 wt%).
To the clear solution (a) , solution (b) and solution (c) were added successively while stirring at 60°C. The batch composition of the synthesis mixture was
7.92 K20 : A1203 : 16.21 Si02 : 1.83 TEAOH : 507 H20. The gel was transferred to 40 ml Teflon lined stainless steel autoclaves. The Si/Al ratio was varied by chang¬ ing the amount of Al-wire dissolved in KOH solution. Crystallization of the gel was carried out under horizontal stirring conditions using a Teflon coated bar magnet at 160°C for 2 to 5 days. When the crystalliza¬ tion was complete, the reaction mixture was washed with distilled water, and the product was recovered by fil- tration. The calcined material as prepared was sub¬ jected to ion-exchange three times with an aqueous IN NH4NO3 solution under reflux, washed with deionized wa¬ ter, dried at 120°C for 3 hours and then calcined at 550°C for 12 hours. The synthesis conditions used are
Figure imgf000009_0001
Table 1: Synthesis conditions used in the crystalliza- tion of SUZ-4 zeolite
*) In the above table, H.S. means horizontal stirring, and SUZ-4a means SUZ-4 + amorphous .
(B) Characterization and catalyst tests X-ray diffraction
The purity and crystallinity of the products were iden¬ tified using X-ray diffraction on a Siemens D-5000 diffractometer with Bragg-Brentano geometry, position sensitive detector and CuK l radiation (λ= 1.5406 A) . X-ray diffraction (XRD) data were analyzed using EVA 8.0, developed by SOCABIM. The diffraction pattern was compared with the data in the powder diffraction file (PDF) database compiled and revised by Joint Committee on Powder Diffraction Standards International Centre. Surface area
The BET surface area of the SUZ-4 catalysts was deter¬ mined by nitrogen adsorption at a temperature of 77 K using a BELSORP-mini II instrument. Prior to the measurement the catalyst was pretreated for 5 hours (out- gassing for 1 hour at 80°C and for 4 hours at 300°C) .
Scanning and transmission electron microscopy
SUZ-4 crystals were sprinkled on a carbon tape mounted on a copper grid. The crystal size and shape were in¬ vestigated using Scanning Electron Microscopy, Quanta 200 F (FEI) . Similarly TEM images were taken and elec- tron diffraction revealed unit cell parameters and ori¬ entation of the 8- and 10-ring channels within the crystal .
The template was removed by calcination under static air at 550°C for 6 hours. The calcined samples were ion-exchanged for 3 x 2 hours with 1M NH4NO3 in a 70 °C water bath. The ion-exchanged catalysts were calcined at 550°C for 2 hours in static air, for 1 hour ex situ in a flow of pure oxygen, and for 1 hour in situ in the fixed bed reactor in a flow of pure oxygen prior to each catalytic experiment to desorb ammonia.
The calcined SUZ-4 catalysts were tested for the MTH reaction using a fixed bed reactor. 50 mg of catalysts and temperatures between 350 and 450 °C were used. The catalysts were pressed, gently crushed and sieved to a particle size of 0.25-0.42 mm. Before each test, the catalysts were calcined in situ at 550°C (see above) under a flow of oxygen for 1 hour. Helium was used as a carrier gas and methanol was fed using a bubble satura- tor placed in a water bath at 20°C. A methanol feed rate (expressed as WHSV, i.e. weight hourly space ve¬ locity, which is defined as the weight of feed flowing per unit weight of the catalyst per hour) of 2.05 gg_1h_1 was used. The reaction products were analyzed by GC and GC-MS .
The GC analyses were performed using an on-line gas chromatograph (Agilent 6890 A with FID) using a Supelco SPB-5 capillary column (60m, 0.530 mm i.d., stationary phase thickness 3ym) . The temperature was programmed between 45 and 260°C with a heating rate of 25 °C min-1 (hold time 5 min at 45°C and 16 min at the final tem¬ perature) . GC-MS analyses were performed using a HP 6890 gas chromatograph equipped with a GS-GASPRO column (60m, 0.32 mm) and a HP-5973 Mass Selective Detector. Each analysis took 40 minutes, and the temperature was programmed between 100 and 250 °C with a heating rate of 10°C min-1 (hold time 10 min at 100°C and 15 min at 250°C) . (c) Results
Fig. 1 displays the XRD profiles of SUZ-4 having Si/Al ratios of 8 and 13 in the synthesis gel. By comparing the observed diffraction profile with a theoretically calculated diffraction profile (Fig.l bottom), it was observed that the product was free from structural im¬ purities . Fig. 2 and Fig. 3 respectively displays the SEM and TEM image of an SUZ-4 zeolite-based catalyst having Si/Al = 8 in the synthesis gel. The crystals were needle-shaped and -2-3 ym in length.
Fig. 3 displays (a) TEM overview micrograph, (b) Micrograph and diffraction image (insert) of random crystallite. Fig. 4 displays the BET isotherm for the SUZ-4 catalyst having Si/Al = 8. The isotherm is typical for a micro- porous material. The surface area of the catalyst was found to be 346 m2/g. Fig. 5 displays GC-MS chromatograms of the methanol to hydrocarbon reaction over different zeolites, reaction carried out under identical conditions.
Example 2
Determination of methanol conversion
Table 2 below shows the percentage methanol conversion and the product selectivities at different reaction temperatures; WHSV = 2.05 gg_1h_1 was used. At 350°C the initial conversion of the catalyst was 83%, and the catalyst showed a very high selectivity for CI (21%, second most abundant species) . Increasing the tempera¬ ture to 400 and 450°C improved the initial conversion by the catalyst to -100%, the selectivity for CI was decreased by approximately a factor of 2. At these re- action temperatures, C2 and C3 were the most abundant species (C2 + C3 > 60%) .
Figure imgf000013_0001
Table 2 : Methanol conversion, product selectivity and C4 hydrogen transfer index of SUZ-4 catalyst for the MTH reaction at different reaction temperatures after 3 minutes on stream, Si/Al = 8. (WHSV = 2.05 gg_1h_1)
It is firmly believed that the high selectivity towards C2 and C3 is caused by the needle-like morphology of the catalyst crystals, as seen by SEM. A simulation of crystal growth indicates that the 10-ring channels run in the direction of the needles. If these needles are described as cylinders, the simulation result means that only the two bases of each cylinder serve as exits through 10-ring channels. The major part of the exter- nal crystal surface will serve as exits through 8- rings, which are orthogonal to the 10-rings. This gives rise to a product shape selectivity dominated by 8- rings, leading to high selectivities towards C2 and C3. The SUZ-4 sample tested deactivates very fast. After 43 minutes (the effluent is sampled every 40 minutes) , the conversion was negligible. This is consistent with the relatively high selectivity towards CI (and also pro- pane) , which is inherently linked to formation of aro- matics and coke. This rapid deactivation may well be attributed to the very high Al content in the sample, which means that the density of acid sites is untypi- cally high for methanol conversion catalysts.
Example 3
Comparison of SUZ-4 to ZSM-5 and SAPO- For the sake of comparison, ZSM-5 and SAPO-34 were tested for the MTH reaction under identical reaction conditions as those of SUZ-4, and the results are pre¬ sented in Fig. 5 and Table 3. Note that SAPO-34 is cur¬ rently used as a commercial MTO catalyst. Table 3 dis- plays the product selectivities for the three different zeolites at 400°C. The GC analyses were performed after 3 minutes on stream, and the catalysts displayed ap¬ proximately 100% conversion. ZSM-5 catalyst has high selectivity for heavier hydrocarbons than SUZ-4 and SAPO-34 catalysts (see Fig. 5 and Table 3) . Catalyst CI C2 C3 C4alkene
ZSM-5 0.28 7.58 21.20 8.77
SUZ-4 10.24 24.35 37.71 14.11
SAPO-34 0.56 29.65 42.59 16.70
Figure imgf000015_0001
Table 3: Product selectivity of the MTH reaction over ZSM-5, SAPO-34, and SUZ-4 catalysts, WHSV = 2, 400°C, and full conversion of methanol
The C4 alkane selectivity of the ZSM-5 catalyst is no¬ tably higher than both that of the inventive SUZ-4 cat- alyst and that of the SAPO-34 catalyst, giving rise to a higher C4 hydrogen transfer index. Except for the selectivity for methane (CI), the SAPO-34 and SUZ-4 cata¬ lysts showed comparable product selectivities for all the other hydrocarbons. For both materials C2 and C3 were the most abundant species (SAPO-34 C2+C3 = 72.3 and SUZ-4 C2+C3 = 61.1). The inventive SUZ-4 catalyst showed a much higher selectivity for methane (approxi¬ mately 10%) than SAPO-34 (>1%) .

Claims

Catalyst for the conversion of oxygenates to ole¬ fins, said catalyst consisting essentially of a se¬ lected SUZ-4 zeolite, characterised in that the zeo¬ lite has a Si/Al ratio of at least 20, preferably between 20 and 500.
Catalyst according to claim 1, characterised in that the zeolite has a Si/Al ratio of between 20 and 100.
A process for the preparation of a catalyst accord¬ ing to claim 1 or 2, said method comprising the steps of:
(a) providing a conventional/standard SUZ-4 zeolite having a Si/Al ratio of less than 20, and
(b) increasing the Si/Al ratio to above 20 by con¬ tacting the product of step (a) with water vapour at elevated temperatures.
Process according to claim 3, characterised in that step (b) is performed at a temperature of 400-700°C.
Process according to claim 3 or 4, characterised in that step (b) is performed for 1-12 hours by feeding 1-20 g ¾0 per g of catalyst per hour.
Process according to any one of claims 3-5, characterised in that the SUZ-4 catalyst resulting from step (b) is washed with an aqueous acid solution.
The use of the catalyst according to claim 1 or 2 in the conversion of oxygenates to olefins.
The use according to claim 7, wherein the oxygenates are selected from the group consisting of CI to C4 alcohols .
9. The use according to claim 8, wherein the oxygenate is methanol.
PCT/EP2012/064300 2011-07-22 2012-07-20 Catalyst for the conversion of oxygenates to olefins and a process for preparing said catalyst WO2013014081A1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
US14/234,370 US9616417B2 (en) 2011-07-22 2012-07-20 Catalyst for the conversion of oxygenates to olefins and a process for preparing said catalyst
CN201280036323.5A CN103842081B (en) 2011-07-22 2012-07-20 For by catalyst of the oxygenate conversion into alkene and the method for preparing the catalyst

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DKPA201100565 2011-07-22
DKPA201100565 2011-07-22

Publications (1)

Publication Number Publication Date
WO2013014081A1 true WO2013014081A1 (en) 2013-01-31

Family

ID=46584007

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2012/064300 WO2013014081A1 (en) 2011-07-22 2012-07-20 Catalyst for the conversion of oxygenates to olefins and a process for preparing said catalyst

Country Status (3)

Country Link
US (1) US9616417B2 (en)
CN (1) CN103842081B (en)
WO (1) WO2013014081A1 (en)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2720990A1 (en) * 2011-06-15 2014-04-23 UT-Battelle, LLC Zeolitic catalytic conversion of alcohols to hydrocarbons
US9181493B2 (en) 2013-07-02 2015-11-10 Ut-Battelle, Llc Catalytic conversion of alcohols having at least three carbon atoms to hydrocarbon blendstock
US9278892B2 (en) 2013-03-06 2016-03-08 Ut-Battelle, Llc Catalytic conversion of alcohols to hydrocarbons with low benzene content
WO2016046296A1 (en) 2014-09-26 2016-03-31 Total Research & Technology Feluy Modified crystalline aluminosilicate for dehydration of alcohols
WO2018046515A1 (en) 2016-09-09 2018-03-15 Total Research & Technology Feluy Process for dehydration of mono-alcohol(s) using a modified crystalline aluminosilicate
US10696606B2 (en) 2016-06-09 2020-06-30 Ut-Battelle, Llc Zeolitic catalytic conversion of alcohols to hydrocarbon fractions with reduced gaseous hydrocarbon content

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2556392B (en) 2016-09-09 2021-04-14 Johnson Matthey Plc JMZ-5 zeolites having an SZR-type crystal structure, and methods of their preparation and use
EP3409837A1 (en) * 2017-06-02 2018-12-05 Benoit Pintat An artificial turf infill material
CN108408735B (en) * 2018-05-21 2021-03-23 太原理工大学 Method for preparing SUZ-4 molecular sieve by using silica fume
CN113617330B (en) * 2021-09-18 2023-04-11 太原理工大学 Low-cost and fast Pb adsorption device 2+ Preparation method of Na-SUZ-4 molecular sieve

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0353915A2 (en) * 1988-08-03 1990-02-07 The British Petroleum Company P.L.C. Novel crystalline (metallo) silicates and germanates
EP0706984A1 (en) 1994-10-12 1996-04-17 BP Chemicals Limited Skeletal isomerization of olefins
US6514470B1 (en) 1999-10-28 2003-02-04 The Regents Of The University Of California Catalysts for lean burn engine exhaust abatement
US6645448B2 (en) 2001-10-18 2003-11-11 General Motors Corporation Hydrothermally stable catalyst for improved lean NOx reduction
WO2008042616A2 (en) 2006-09-29 2008-04-10 Uop Llc Integrated processing of methanol to olefins
EP1963241A2 (en) 2005-12-22 2008-09-03 Uop Llc Methanol-to-olefins process with reduced coking
JP2009233620A (en) 2008-03-28 2009-10-15 Tosoh Corp Catalyst for scr and purification method of nitrogen oxide using it
JP2011062664A (en) * 2009-09-18 2011-03-31 Tosoh Corp Adsorbent containing suz-4 zeolite for hydrocarbon in exhaust gas of automobile, and method for adsorption removal of hydrocarbon

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6768035B2 (en) 2002-01-31 2004-07-27 Chevron U.S.A. Inc. Manufacture of high octane alkylate
DE102005015923B4 (en) * 2005-04-06 2014-12-04 Air Liquide Global E&C Solutions Germany Gmbh Process for the preparation of C2 to C4 olefins from an oxygenate and steam containing feed stream
WO2007105875A1 (en) 2006-03-10 2007-09-20 Korea Research Institute Of Chemical Technology Preparing method of light olefin trimers and production of heavy alkylates by using thereof

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0353915A2 (en) * 1988-08-03 1990-02-07 The British Petroleum Company P.L.C. Novel crystalline (metallo) silicates and germanates
US5118483A (en) 1988-08-03 1992-06-02 The British Petroleum Company P.L.C. Crystalline (metallo) silicates and germanates-suz-4
EP0706984A1 (en) 1994-10-12 1996-04-17 BP Chemicals Limited Skeletal isomerization of olefins
US6514470B1 (en) 1999-10-28 2003-02-04 The Regents Of The University Of California Catalysts for lean burn engine exhaust abatement
US6645448B2 (en) 2001-10-18 2003-11-11 General Motors Corporation Hydrothermally stable catalyst for improved lean NOx reduction
US6936562B2 (en) 2001-10-18 2005-08-30 General Motors Corporation Hydrothermally stable catalyst for improved lean NOx reduction
EP1963241A2 (en) 2005-12-22 2008-09-03 Uop Llc Methanol-to-olefins process with reduced coking
WO2008042616A2 (en) 2006-09-29 2008-04-10 Uop Llc Integrated processing of methanol to olefins
JP2009233620A (en) 2008-03-28 2009-10-15 Tosoh Corp Catalyst for scr and purification method of nitrogen oxide using it
JP2011062664A (en) * 2009-09-18 2011-03-31 Tosoh Corp Adsorbent containing suz-4 zeolite for hydrocarbon in exhaust gas of automobile, and method for adsorption removal of hydrocarbon

Non-Patent Citations (6)

* Cited by examiner, † Cited by third party
Title
ASENSI M A ET AL: "Zeolite SUZ-4: reproducible synthesis, physicochemical characterization and catalytic evaluation for the skeletal isomerization of n-butenes", MICROPOROUS AND MESOPOROUS MATERIALS, ELSEVIER SCIENCE PUBLISHING, NEW YORK, US, vol. 28, no. 3, 1 May 1999 (1999-05-01), pages 427 - 436, XP004165644, ISSN: 1387-1811, DOI: 10.1016/S1387-1811(98)00314-X *
AYYAPPAN SUBBIAH ET AL: "NOx reduction over metal-ion exchanged novel zeolite under lean conditions: activity and hydrothermal stability", APPLIED CATALYSIS. B, ENVIRONMENTAL, vol. 42, no. 2, 1 May 2003 (2003-05-01), pages 155 - 178, XP055043866, ISSN: 0926-3373, DOI: 10.1016/S0926-3373(02)00230-8 *
JIANG S ET AL: "Effect of dealumination on acidic and catalytic properties of HK-SUZ-4", DALIAN HAISHI DAXUE XUEBAO, DALIAN HAISHI DAXUE CHUBANSHE, CN, vol. 33, no. 4, 1 November 2007 (2007-11-01), pages 118 - 121, XP009164436, ISSN: 1006-7736 *
JIANG,S. ET AL., CHEMISTRY LETTERS, vol. 33, no. 8, 2004, pages 1048
S. JIANG ET AL., CHEMISTRY LETTERS, vol. 33, no. 8, 2004, pages 1048
SHAN JIANG: "Zeolite SUZ-4 as Selective Dehydration Catalyst for Methanol Conversion to Dimethyl Ether", CHEMISTRY LETTERS, CHEMICAL SOCIETY OF JAPAN, JP, vol. 33, no. 8, 1 January 2004 (2004-01-01), pages 1048 - 1049, XP009164437, ISSN: 0366-7022 *

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2720990A4 (en) * 2011-06-15 2014-12-24 Ut Battelle Llc Zeolitic catalytic conversion of alcohols to hydrocarbons
US9533921B2 (en) 2011-06-15 2017-01-03 Ut-Battelle, Llc. Zeolitic catalytic conversion of alochols to hydrocarbons
US11773333B2 (en) 2011-06-15 2023-10-03 Ut-Battelle, Llc Zeolitic catalytic conversion of alcohols to hydrocarbons
EP2720990A1 (en) * 2011-06-15 2014-04-23 UT-Battelle, LLC Zeolitic catalytic conversion of alcohols to hydrocarbons
US9938467B2 (en) 2011-06-15 2018-04-10 Ut-Battelle, Llc Zeolitic catalytic conversion of alcohols to hydrocarbons
US9278892B2 (en) 2013-03-06 2016-03-08 Ut-Battelle, Llc Catalytic conversion of alcohols to hydrocarbons with low benzene content
US9434658B2 (en) 2013-03-06 2016-09-06 Ut-Battelle, Llc Catalytic conversion of alcohols to hydrocarbons with low benzene content
US9181493B2 (en) 2013-07-02 2015-11-10 Ut-Battelle, Llc Catalytic conversion of alcohols having at least three carbon atoms to hydrocarbon blendstock
US9944861B2 (en) 2013-07-02 2018-04-17 Ut-Battelle, Llc Catalytic conversion of alcohols having at least three carbon atoms to hydrocarbon blendstock
US10512903B2 (en) 2014-09-26 2019-12-24 Total Research & Technology Feluy Modified crystalline aluminosilicate for dehydration of alcohols
WO2016046296A1 (en) 2014-09-26 2016-03-31 Total Research & Technology Feluy Modified crystalline aluminosilicate for dehydration of alcohols
US10696606B2 (en) 2016-06-09 2020-06-30 Ut-Battelle, Llc Zeolitic catalytic conversion of alcohols to hydrocarbon fractions with reduced gaseous hydrocarbon content
WO2018046516A1 (en) 2016-09-09 2018-03-15 Total Research & Technology Feluy Catalyst composition comprising modified crystalline aluminosilicate for dehydration of alcohols
US10851028B2 (en) 2016-09-09 2020-12-01 Total Research & Technology Feluy Process for dehydration of mono-alcohol(s) using a modified crystalline aluminosilicate
US10899682B2 (en) 2016-09-09 2021-01-26 Total Refining & Technology Feluy Catalyst composition comprising modified crystalline aluminosilicate for dehydration
WO2018046515A1 (en) 2016-09-09 2018-03-15 Total Research & Technology Feluy Process for dehydration of mono-alcohol(s) using a modified crystalline aluminosilicate

Also Published As

Publication number Publication date
CN103842081A (en) 2014-06-04
US9616417B2 (en) 2017-04-11
CN103842081B (en) 2018-06-12
US20140179971A1 (en) 2014-06-26

Similar Documents

Publication Publication Date Title
US9616417B2 (en) Catalyst for the conversion of oxygenates to olefins and a process for preparing said catalyst
EP2860158A1 (en) Metal silicoaluminophosphate molecular sieve having rho skeleton structure and preparation process therefor
EP2794525B1 (en) Aromatic transformation using uzm-39 aluminosilicate zeolite
JP5588973B2 (en) Method for producing crystalline metallosilicate
JP6005878B2 (en) Aromatic transalkylation reaction using UZM-39 aluminosilicate zeolite
Park et al. Hydrocarbon synthesis through CO2 hydrogenation over CuZnOZrO2/zeolite hybrid catalysts
JP2021516610A (en) Method for Producing Composite Zeolite Catalyst for Heavy Reformate Conversion to Xylene
KR20210098543A (en) Catalysts for the production of light olefins from C4-C7 hydrocarbons
JP5668422B2 (en) Method for producing aluminosilicate
JP2021516609A (en) Method for Producing Composite Zeolite Catalyst for Heavy Reformate Conversion to Xylene
EP2448890A2 (en) Process for alkylation of aromatic hydrocarbons using uzm-35
NO174621B (en) Procedure for converting a c4-c6 n-olefin to an iso-olefin
KR20200126984A (en) Catalyst systems useful for dehydrogenation reactions
US4537757A (en) Crystalline aluminosilicate AZ-1 and a process for producing the same
CN110997143A (en) Composition comprising a mixed metal oxide and a moulded article comprising a zeolitic material having a framework type CHA and an alkaline earth metal
US5397561A (en) Zeolite-type material
WO2019177957A1 (en) Method of heavy reformate conversion into btx over metal-impregnated zsm-5+ssz-33 zeolite composite catalyst
Shin et al. Comparative study of CHA-and AEI-type zeolytic catalysts for the conversion of chloromethane into light olefins
WO2020244630A1 (en) Direct synthesis of aluminosilicate zeolitic materials of the iwr framework structure type and their use in catalysis
KR20150122158A (en) Zeolite ssz-57 having enhanced large pore selectivity
Xu et al. Conversion of methanol to propylene over a high silica B-HZSM-5 catalyst
WO2019177961A1 (en) Method of heavy reformate conversion into btx over metal-impregnated zsm-5+nanocrystalline beta zeolite composite catalyst; said composite catalyst
CN111295243A (en) Catalyst for producing olefin by dehydrogenation of alkane and method for producing olefin using said catalyst
WO2018236471A1 (en) Olefin oligomerization processes and related zeolites and structure directing agents
WO2022270401A1 (en) Method for producing cyclopentadiene

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 12740562

Country of ref document: EP

Kind code of ref document: A1

DPE1 Request for preliminary examination filed after expiration of 19th month from priority date (pct application filed from 20040101)
NENP Non-entry into the national phase

Ref country code: DE

WWE Wipo information: entry into national phase

Ref document number: 14234370

Country of ref document: US

122 Ep: pct application non-entry in european phase

Ref document number: 12740562

Country of ref document: EP

Kind code of ref document: A1